Heteroaroyl-Substituted Serineamides

Abstract

The present invention relates to heteroaroyl-substituted serinamides of the formula I in which the variables A, Het and R 1 to R 5 are as defined in the description, and to their agriculturally useful salts, to processes and intermediates for their preparation, and to the use of these compounds or of the compositions comprising these compounds for controlling unwanted plants.

1 . A compound which is a heteroaroyl-substituted serineamide of the formula I  
       
         
           
           
               
               
           
         
       
       in which the variables are as defined below: 
 A is 5- or 6-membered heteroaryl having one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom, which heteroaryl may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl;  
 Het is mono- or bicyclic heteroaryl having 5 to 10 ring members comprising 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, which heteroaryl may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkoxy, amino, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -haloalkylsulfonylamino, aminocarbonylamino, (C 1 -C 6 -alkylamino)carbonylamino, di-(C 1 -C 6 -alkyl)aminocarbonylamino, aryl and aryl-(C 1 -C 6 -alkyl);  
 R 1 , R 2  are independently hydrogen, hydroxyl or C 1 -C 6 -alkoxy;  
 R 3  is C 1 -C 6 -alkyl, C 1 -C 4 -cyanoalkyl or C 1 -C 6 -haloalkyl;  
 R 4  is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 -haloalkynyl, formyl, C 1 -C 6 -alkylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 2 -C 6 -alkynylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 3 -C 6 -alkenyloxycarbonyl, C 3 -C 6 -alkynyloxycarbonyl, C 1 -C 6 -alkylaminocarbonyl, C 3 -C 6 -alkenylaminocarbonyl, C 3 -C 6 -alkynylaminocarbonyl, C 1 -C 6 -alkylsulfonylaminocarbonyl, di-(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkenyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 1 -C 6 -alkoxy)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkenyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl, N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl, di-(C 1 -C 6 -alkyl)aminothiocarbonyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl, N—(C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl, N-(di-C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl or tri-C 1 -C 4 -alkylsilyl, 
 where the alkyl, cycloalkyl and alkoxy radicals mentioned may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, hydroxyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di-(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkyl-C 1 -C 6 -alkoxycarbonylamino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy;  
 
 phenyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenoxycarbonyl, phenylaminocarbonyl, phenylsulfonylaminocarbonyl, N—(C 1 -C 6 -alkyl)-N-(phenyl)aminocarbonyl, phenyl-C 1 -C 6 -alkylcarbonyl, heterocyclyl, heterocyclyl-C 1 -C 6 -alkyl, heterocyclylcarbonyl, heterocyclylcarbonyl-C 1 -C 6 -alkyl, heterocyclyloxycarbonyl, heterocyclylaminocarbonyl, heterocyclylsulfonylaminocarbonyl, N—(C 1 -C 6 -alkyl)-N-(heterocyclyl)aminocarbonyl, or heterocyclyl-C 1 -C 6 -alkylcarbonyl, 
 where the phenyl and the heterocyclyl radical of the 17 last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy; or  
 
  SO 2 R 6 ;  
 R 5  is hydrogen or C 1 -C 6 -alkyl;  
 R 6  is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or phenyl, 
 where the phenyl radical may be partially or fully halogenated and/or may carry one to three of the following groups: C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or C 1 -C 6 -alkoxy;  
 or an agriculturally useful salt thereof.  
 
 
     
     
         2 . The compound according to  claim 1  where A is 5- or 6-membered heteroaryl selected from the group consisting of pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, tetrazolyl, pyridyl and pyrimidinyl; where the heteroaryl radicals mentioned may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl.  
     
     
         3 . The compound according to  claim 1 , where Het is mono- or bicyclic heteroaryl selected from the group consisting of furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, quinolinyl and indolyl, 
 where the heteroaryl radicals mentioned may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of nitro, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, hydroxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkoxy, amino, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, C 1 -C 4 -alkylsulfonylamino, C 1 -C 4 -haloalkylsulfonylamino, aminocarbonylamino, (C 1 -C 4 -alkylamino)carbonylamino and di-(C 1 -C 4 -alkyl)aminocarbonylamino.    
     
     
         4 . The compound according to  claim 1  where R 1 , R 2  and R 5  are hydrogen.  
     
     
         5 . A process for preparing a heteroaroyl-substituted serineamide[s] of the formula I according to  claim 1 , wherein a serine derivative[s] of the formula V  
       
         
           
           
               
               
           
         
       
       where Het and R 1 , R 4  and R 5  are as defined in  claim 1  and L 1  is a nucleophilically displaceable leaving group  
       is reacted with a heteroaryl acid (derivative[s]) of the formula IV  
       
         
           
           
               
               
           
         
       
       where A is as defined  claim 1  and L 2  is a nucleophilically displaceable leaving group to give the corresponding heteroaroyl derivative[s] of the formula IV  
       
         
           
           
               
               
           
         
       
       where A, Het, R 1 , R 4  and R 5  are as defined in  claim 1  and L 1  is a nucleophilically displaceable leaving group,  
       and the resulting heteroaroyl derivative[s] of the formula III &F is then reacted with an amine of the formula II  
         HNR 2 R 3   II,  where R 2  and R 3  are as defined in  claim 1  to produce a heteroaroyl-substituted serineamide of formula 1.    
     
     
         6 . A process for preparing a heteroaroyl-substituted serineamide[s] of the formula I according to  claim 5  where R 4  and R 5  are hydrogen, wherein a heteroaroyl derivative[s] of the formula III where R 4  and R 5  are hydrogen is prepared by acylating a keto compound[s] of the formula XIII  
       
         
           
           
               
               
           
         
       
       where R 1  is as defined in  claim 5  and L 1  is a nucleophilically displaceable leaving group  
       with a heteroaryl acid (derivatives) of the formula IV to give a N-acyl keto compound[s] of the formula XII  
       
         
           
           
               
               
           
         
       
       where A, Het and R 1  are as defined in  claim 5  and L 1  is a nucleophilically displaceable leaving group  
       and subsequently reducing of the keto group to produce the heteroaroyl derivative of formula III.  
     
     
         7 . A heteroaroyl derivative of the formula III  
       
         
           
           
               
               
           
         
       
       wherein 
 A is 5- or 6-membered heteroaryl having one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom, which heteroaryl may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl;  
 Het is mono- or bicyclic heteroaryl having 5 to 10 ring members comprising 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, which heteroaryl may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of cyan, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkoxy, amino, C 1 -C 6 -alkylamino, di-(C 1 -C 6 -alkyl)amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -haloalkylsulfonylamino, aminocarbonylamino. (C 1 -C 6 -alkylamino)carbonylamino, di-(C 1 -C 6 -alkyl)aminocarbonylamino, aryl and aryl-(C 1 -C 6 -alkyl);  
 R 1  is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl;  
 R 4  is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkenyl, C 1 -C 6 -haloalkynyl, formyl, C 1 -C 6 -alkylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 1 -C 6 -alkynylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 3 -C 6 -alkenyloxycarbonyl, C 3 -C 6 -alkynyloxycarbonyl, C 1 -C 6 -alkylaminocarbonyl, C 3 -C 6 -alkenylaminocarbonyl, C 3 -C 6 -alkynylaminocarbonyl, C 1 -C 6 -alkylsulfonylaminocarbonyl, di-(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 1 -C 6 -alkenyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 1 -C 6 -alkoxy)-N—(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 3 -C 6 -alkenyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl. N—(C 3 -C 6 -alkynyl)-N—(C 1 -C 6 -alkoxy)aminocarbonyl, di-(C 1 -C 6 -alkyl)aminothiocarbonyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl. N—(C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl, N-(di-C 1 -C 6 -alkylamino)imino-C 1 -C 6 -alkyl or tri-C 1 -C 4 -alkylsilyl, 
 where the alkyl, cycloalkyl and alkoxy radicals mentioned may be partially or fully halogenated and/or may carry one to three of the following groups:  
 cyano, hydroxyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4  alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di-(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkyl-C 1 -C 6 -alkoxycarbonylamino, C 1 -C 4 -alkylcarbonyl,  
 hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4  alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy;  
 
 phenyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenoxycarbonyl. Phenylaminocarbonyl. Phenylsulfonylaminocarbonyl. N—(C 1 -C 6 -alkyl)-N-(phenyl)aminocarbonyl, phenyl-C 1 -C 6 -alkylcarbonyl, heterocyclyl, heterocyclyl-C 1 -C 6 -alkyl, heterocyclylcarbonyl, heterocyclylcarbonyl-C 1 -C 6 -alkyl, heterocyclyloxycarbonyl, heterocyclylaminocarbonyl,  
 heterocyclylsulfonylaminocarbonyl. N—(C 1 -C 6 -alkyl)-N-(heterocyclyl)-aminocarbonyl, or heterocyclyl-C 1 -C 6 -alkylcarbonyl, 
 where the phenyl and the heterocyclyl radical of the 17 last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy; or  
 
 SO 2 R 6 ;  
 R 5  is hydrogen or C 1 -C 6 -alkyl;  
 and L 1  is a nucleophilically displaceable leaving group.  
 
     
     
         8 . A composition, comprising a herbicidally effective amount of at least one heteroaroyl-substituted serineamide of the formula I or an agriculturally useful salt thereof according to  claim 1  and auxiliaries customary for formulating crop protection agents.  
     
     
         9 . A process for preparing a herbicidal composition comprising mixing a herbicidally effective amount of at least one heteroaroyl-substituted serineamide of the formula I or an agriculturally useful salt thereof according to  claim 1  and auxiliaries customary for formulating crop protection agents are mixed.  
     
     
         10 . A method for controlling unwanted vegetation, wherein a herbicidally effective amount of at least one heteroaroyl-substituted serineamide of the formula I or an agriculturally useful salt thereof according to  claim 1  is allowed to act on plants, their habitat and/or on seed.  
     
     
         11 . (canceled)  
     
     
         12 . The compound of  claim 1 , wherein 
 A is 5- or 6-membered heteroaryl which is attached via carbon and selected from the group consisting of A1 to A14                                           where the arrow indicates the point of attachment and    R 7  is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl;    R 8  is halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or C 1 -C 6 -haloalkoxy;    R 9  is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl;    R 10  is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl or C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl;    
     
     
         13 . The compound of  claim 3 , wherein Het is selected from the group consisting of thienyl, thiazolyl, tetrazolyl, pyridyl and indolyl, 
 where the heteroaryls mentioned may be partially or fully halogenated and/or may carry 1 to 2 radicals selected from the group consisting of nitro, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, hydroxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkoxy, amino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylsulfonylamino, C 1 -C 4 -haloalkylsulfonylamino, aminocarbonylamino, (C 1 -C 4 -alkylamino)carbonylamino and di-(C 1 -C 4 -alkyl)aminocarbonylamino.    
     
     
         14 . The compound of  claim 3 , wherein Het is Het-1, Het-2, Het-3, Het-4, Het-5 or Het-6;  
       
         
           
           
               
               
           
         
       
       where the arrow indicates the point of attachment and 
 R 11  is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl;  
 R 12  is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; and  
 R 13  is hydrogen, halogen or C 1 -C 4 -alkyl;  
 
     
     
         15 . The compound of  claim 1 , wherein 
 R 1  is hydrogen;    R 2  is hydrogen or hydroxyl; and    R 3  is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl.    
     
     
         16 . The compound of  claim 15 , wherein R 4  is 
 R 4  is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -alkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylaminocarbonyl, C 1 -C 6 -alkylsulfonylaminocarbonyl, di-(C 1 -C 6 -alkyl)aminocarbonyl, N—(C 1 -C 6 -alkoxy)-N—(C 1 -C 6 -alkyl)aminocarbonyl, di-(C 1 -C 6 -alkyl)-aminothiocarbonyl, C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl,    where the alkyl, cycloalkyl and alkoxy radicals mentioned may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, hydroxyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di-(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)aminocarbonyl, or C 1 -C 4 -alkylcarbonyloxy; phenyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenylsulfonylaminocarbonyl or phenyl-C 1 -C 6 -alkylcarbonyl,    where the phenyl radical of the 6 last-mentioned substituents may be partially or fully halogenated and/or may carry one to three of the following groups: nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy; or    SO 2 R 6 .    
     
     
         17 . The compound of  claim 1 , wherein 
 A is 5- or 6-membered heteroaryl selected from the group consisting of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and pyridyl;    where the heteroaryl radicals mentioned may be partially or fully halogenated and/or may carry 1 to 3 radicals selected from the group consisting of C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl and C 1 -C 6 -haloalkyl;    Het is mono- or bicyclic heteroaryl selected from the group consisting of thienyl, thiazolyl, tetrazolyl, pyridyl and indolyl,    where the heteroaryls mentioned may be partially or fully halogenated and/or may carry 1 to 2 radicals selected from the group consisting of nitro, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, hydroxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkoxy, amino, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)amino, C 1 -C 4 -alkylsulfonylamino, C 1 -C 4 -haloalkylsulfonylamino, aminocarbonylamino, (C 1 -C 4 -alkylamino)carbonylamino and di-(C 1 -C 4 -alkyl)aminocarbonylamino;    R 1  and R 2  are hydrogen;    R 3  is C 1 -C 4 -alkyl,    R 4  is hydrogen, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkylaminocarbonyl, di-(C 1 -C 4 -alkyl)-aminocarbonyl, phenylaminocarbonyl, N—(C 1 -C 4 -alkyl)-N-(phenyl)aminocarbonyl, SO 2 CH 3  or SO 2 (C 6 H 5 ); and    R 5  is hydrogen.    
     
     
         18 . The method of  claim 10 , wherein the heteroaroyl-substituted serineamide or salt thereof is applied at a rate of application of 0.001 to 3.0 kg/ha.  
     
     
         19 . The method of claims  18 , wherein the amount is 0.01 to 1.0 kg/ha.